Photographic light-sensitive silver halide material containing azo dyes

ABSTRACT

PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL, ESPECIALLY FOR THE SILVER DYESTUFF BLEACHING PROCESS, CONTAINING AN AZO DYESTUFF DERIVED (A) FROM A TETRAZO COMPOUND OF A DIAMINE THE AMINO GROUPS OF WHICH ARE BOUND TO BENZENE RADICALS WHICH ARE LINKED TOGETHER IN AMIDE-LIKE MANNER BY AN ORGANIC BRIDGE MEMBER AND (B) 2-PHENYLAMINO-8HYDROXY-MONO- OR -DISULPHONIC ACIDS, THE PHENYL REDISUES CONTAINING AT LEAST ONE FURTHER SUBSTITUENT, BUT BEING UNSUBSTITUTED IN AT LEAST ONE POSITION ORTHO TO THE -NHGROUP. THESE MAGENTA DYESTUFFS ARE FAST TO DIFFUSION, EASILY SOLUBLE IN WATER, INSENSITIVE TO CALCIUM IONS AND COMPLETELY BLEACHABLE TO WHITE.

United States Patent 3,749,576 PHOTOGRAPHIC LIGHT-SENSITIVE SILVERHALIDE MATERIAL CONTAINING AZO DYES Bernhard Piller, Marly-le-Petit,Switzerland, assignor to Ciba-Geigy AG, Basel, Switzerland No Drawing.Filed May 4, 1971, Ser. No. 140,275 Claims priority, applicationSwitzerland, May 5, 1970, 6,689/70 Int. Cl. G03c 1/10 US. Cl. 9699 8Claims The subject of the invention are azo dyestuffs of the formula inwhich X and X are a sulphonic acid group or preferably a hydrogen atom,A and A are each a benzene radical, possibly substituted with halogen,low alkyl, low alkoxy or sulphonyl (sulphonic acid gro p), R and R areeach a halogen atom, a possibly substituted 10W alkyl, low alkoxy,phenoxy, low alkylcarbonyl, carboxylic acid amide, low alkylsulphonylgroup or sulphonic acid amide group or a carboxylic or sulphonic acidgroup, R and R are each a hydrogen or halogen atom, a low alkoxy orsulphonic acid group and M is an amide-like organic radical bound to Aand A the azo groups present in the molecule being arranged in the formof a straight chain.

There are to be understood by low groups of the indicated type thosewith at the most four carbon atoms. Dyestuffs with a linear arrangementof the azo groups are those which contain all azo groups in thefollowing schematic arrangement:

M can be an aliphatic, aromatic or heterocyclic radical, which is boundafter the manner of an amide to A and A or the diamide radicals ofcarbonic or oxalic acid.

ice

Radicals M bound after the manner of an amide thus correspond to thefollowing formulae:

M represents here an organic radical of the-indicated type and M","is aheterocyclic radical having an acid character, such as, e.g., a cyanuricacid radical (1,3,5- triazine radical).

The radicals R and R can possibly be substituted further, alkylradicals, e.g., by halogen atoms as in the case of the trifluoromethylgroup, carboxylic and sulphonic acid amide radicals by one or two alkylgroups with at the most 4 carbon atoms each.

The dyestuffs of Formula 1 can be both symmetrical and asymmetrical.

Preferred azo dyestuffs correspond to the formula in which M is an acidamide-like organic radical (-CO--NH, SO -NH) bound to A and A and X X AA R R R and R have the meaning indicated.

Of special interest here are azo dyestuffs of the formula in which M isa diamide radical of an at least dibasic acid of organic naturecontaining carbon, which is bound by the amide nitrogen atoms to A and Aand X X A A R R R and R have the meaning indicated.

The organic acids from which the radical M is derived are aliphatic, inparticular however aromatic or hetero- (5) Hogs SO H OH HO- -N=NA M -A1--N=N-- I l I X, NH HN X R1 R3 R1 R3 and, above all, those of theformula OH HO- N=NA.;Mz-A N=N 1TH H1 1 Q Q R1 R2 1 R2 in which X A R Rand M have the meaning indicated, have proved particularly suitable.

Azo dyestulfs of the formula 1163' SIOQH OH HO IiIH S0311 HOQ S HN 11MB:R1 R2 claim a special interest; R R and M have the indicated meaning inthem. Advantageous properties are, for example, shown by the azodyestuffs of the formula H 038 S 3H OH HO 1%IH S 0311 H038 HN I 02 XX RR R5 R5 in which R is a hydrogen or halogen atom, a methyl, methoxy orsulphonic acid group and R is a sulphonic acid group, a methyl carbonylgroup or a halogen atom, at most one of the radicals R and Rrepresenting a sulphonic acid group and M having the indicated meaning.

As particularly advantageous are to be considered the dyestuffs of theformula H 0 315 S 0 all 0 H H H HO 5 i i! l NH 5 0 3H H 03 s HN R7 R3 R7R5 1. in which R7 is a halogen atom with an atomic number less than 5 3,a trifluoromethyl group, a methyl carbonyl group, a methyl sulphonegroup, a sulphonic acid group or a methoxy group, R a hydrogen atom, ahalogen atom with an atomic number less than 53 or a methyl group and Mhas the meaning indicated.

Further preferred azo dyestuifs correspond to the formula E038 SOaH OHM2 HO- NH SOzH HOs S HN l l I o R5 R6 5 u and, in particular, to theformula OH 4 lTTH-Mr-HN HO- N: N=N- .5 Q Q NH 03H H038 HN T H xx R5 R5R5 R5 in which M is a carbonyl group (-CO) or a heterocyclic orcarbocyclic aromatic dicarbonyl radical and M in which M is a carbonylgroup, a terephthaloyl, isophthaloyl, benzophenone-4,4-dicarbonyl,diphenylsulphone-4,4'-dicarbonyl, azobenzene-3,3'-dicarbonyl,thiophene2,4-dicarbonyl or pyridine-2,6 or 3,5-dicarbonyl 5 radical andR and R have the indicated meaning, are particularly suitable.

Furthermore, disazo dyestuffs of the formula on n NH-Ma-NH K Mg QM I TH013 E0: HN

87 RI Br RI are preferred, in which M is a CO+ group or a benzene,benzophenone, diphenylsulphone, diphenyl urea, thiophene or pyridineradical attached to the NH groups in each case by a -CO group, themembers of said ring systems attached to the two CO groups beingseparated from one another by at least one further ring member, and inwhich R and R have the indicated meaning.

Amongst the dyestuffs of Formula 12 there are, e.g. suitable those-ofthe formula 03 NrHm-HN H0 Nfl N=N I JK HO 1 05K H Bl C1 30 CI in which Ris a hydrogen or chlorine atom or a methyl group and M has the indicatedmeaning.

Also of interest are disazo dyestuffs of the formula in which M is aterephthaloyl, isophthaloyl, pyridine-2,6- or -3,5-dicarbonyl orthiophene- 2,5-dicarbonyl radical.

There may also be mentioned as particularly outstanding embodimentsdyestuffs of the formula EN-O C E0 QM in which R represents one of theradicals of the formulae OC-CH 10 as well as those of the formula son;

mz-o c-m-co-nu no Q QNE-IN nos in which M is a pyridine radical arrangedsymmetrically in relation to the bonds to the CO groups, and R is one ofthe radicals of the formulae CH3 0 and Q 1 The dyestuffs of the Formulael to 17 can exist not only as indicated in the form of their free acids,i.e. with H0 5 and/or HOOC groups, but also as salts. Depending on theconditions of separation, e.g. the selected pH value or the cation,which the salt used for separation has, the acid groups can be an AOcation and/or a COO cation, such as, e.g. SO Na, SO K,

(SO Ca, COONa, COOLi, COONH It is preferably therefore a matter of saltsof the alkaline earth or, in particular, alkali metal group.

The radicals of the formulae and 60 in Formula 1 are derived, e.g. fromcompounds of the following formulae:

(19.1) 110315 (19.2) HO IS (19.23) HOaS 19.24 H038 gofi l NH NH l QCHzCHI SOaH s02N 80H OH I NE NH Y CH3 I CH3 50 11 19.27 HOaS Hoa I IHwas I HOaS- -OH 11TH QCl 2)3-' l (19.29) SIOaH HOaS- OH 10 The radicalsA and A as well as A -MA in Formula l are derived, e.g. from thefollowing compounds:

1-amino-4-nitrobenzene, 1-amino-4-nitrobenzene-2-sulphonic acid,l-amino-4-nitrobenzene-3-sulphonic acid,1-amino-5-nitro'benzene-2-sulphonic acid,1-amino-4-acetylaminobenzene-Z-sulphonic acid,l-amino-5-acetylaminobenzene-2-sulphonic acid,l-amino-2-methyl-4-nitrobenzene, 1-amino-2-methoxy-4-nitrobenzene,1-arnino-2-chloro-4-nitrobenzene,1-amino-5-methyl-4-nitrobenzene-Z-sulphonic acid,l-amino-2,5-dimethoxy-4-nitrobenzene, l-amino-Z-tertiarybutyl-4-nitrobenzene, 1-amino-2-n-butoXy-4-nitrobenzene.

NH-O 0 -NO;

(20. 3) OCH};

1 HeNONH-COCH:

SOsH (20.4)

mNOo 04130-0 C-HN-ONH:

The radical M in Formula 1 is derived from anhydrides and, inparticular, from halides of at least dibasic acylation components.

There may, e.g. be mentioned as anhydrides:

succinic acid anhydride, chlorosuccinic acid anhydride or glutaric acidanhydride.

The radical M is, however, preferably derived from dihalides, namely,e.g, from:

4,4'-dichloro-azobenzene-3,3'-dicarboxylic acid dichloride,azobenzene-4,4'-dicarboxylic acid dichloride,2,2-dimethylazobenzene5,5'-dicarboxylic acid dichloride,2,2'-dimethoxyazobenzene-5,S'-dicarboxylic acid dichloride,pyrrole-2,5-dicarboxylic acid dichloride,2,2'-dichloroazobenzene-5,5'-dicarboxylic acid dichloride,2,Z'-dimethylazobenzene-4,4'-dicarboxylic acid dichloride,4-methoxyazobenzene-3,4-dicarboxylic acid dichloride,N,N'-diphenyl-urea-4,4-dicarboxylic acid dichloride,3,3'-dichloroazobenzene4,4-dicarboxylic acid dichloride,4-rnethoxyazobenzene-3,4'-dicarboxylic acid dichloride,azobenzene-4,4'-disulphonic acid dichloride, azobenzene-3,3'-disulphonicacid dichloride, diphenylsulphone-4,4'-dicarboxylic acid dichloride,benzene-1,3-disulphonic acid dichloride,diphenylmethane-4,4'-dicarboxylic acid dichloride,diphenylsulphide-4,4'-dicarboXylic acid dichloride,4,6-dichloropyrimidine, 1-phenyl-3,5-dichloro-2,4,6-triazine,1-meth0xy-3,5-dichloro'2,4,6-triazine, diphenylketone-3,4'- or4,4'-dicarboxylic acid dichloride.

In addition, cyanuryl chloride also comes under consideration.

The dyestufifs of Formula 1 can be prepared by various known processes.An initial process is characterized in that at least one compound of theformula is reacted with a halide or anhydride of an acid of the formula(22) HOZ M'--Z -OH is coupled with at least one compound of the formula(24) HOaS in which An in a q-valent anion and q is 1 or 2, and A A X M,R and R have the indicated meaning.

A third method is also characterized in that a diazonium salt of theformula in which An q, A A M, R R and X have the indicated meaning, iscoupled with a compound of Formula 24.

In the first method, it is desirable to proceed by diazotising acompound of one of the formulae (26.1) H N-A --NO (26.2) H N-A NO (26.3H N-A NH-D or (26.4) H N-A -NH-D in which A, and A have the indicatedmeaning and D is a protective group capable of being split ed, andcoupling in an acid medium with a compound of Formula 18.1 or 18.2.After reduction of the nitro group and/or splitting off of theprotective group, there is obtained the compound of the formula in whichA A R R R R X andX have the indicated meaning. It is now possible eitherto link 2 mols of the compound of Formula 27.1 or 27.2 with 1 mol bridgemember, e.g. of the formula (29) H NA M--A -NH e.g., one of thecompounds of the Formulae 20.4, 20.5

or 20.6 and couple with 2 mols compound of Formula 18.1 or 18.2 to thedyestutf of Formula 1.

Finally, it is also possible in the third method to diazotise a compoundof the formula e.g., the compound of Formula 20.2, to couple in an acidmedium with a compound of Formula 18.1, to reduce the nitro group and/or split off the protective group and, after renewed diazotisation andcoup'ing with a.

compound of Formula 18.1 or 18.2, to obtain the dyestuff of Formula 1.

The condensation of amines with acid halides and anhydride takes placeaccording to known methods and is desirably undertaken in a polarsolvent such as water or in a polar organic solvent, such as pyridine,methanol, glycol, diethylacetamide, dimethylformamide orN-rnethylpyrrolidone.

It can also be advantageous to condense in the presence of acid-bindingagents, such as e.g. alkali carbonates. Basic solvents such as pyridineor, in particular, N-methylpyrrolidone themselves act in an acid-bindingmanner.

The dyestuffs of Formula 1 can be used for various purposes, e.g. inphotographic, light-sensitive materials, being 'here particularly usefulas image dyestuffs for the silver colour bleaching process. Accordingly,valuable photographicmaterials can be prepared in the customary andknown manner which contain on a support at least one layer with adyestufi of Formula 1.

In particular, these dyestuffs can be present in a multiple layermaterial which contains on a layer support a selectively red-sensitivelayer dyed with a green-blue dyestuff, on it a selectivelygreen-sensitive layer dyed purple with a dyestuff of Formula 1 andfinally a blue-sensitive layer dyed with a yellow dyestuff. It ishowever also possible to embed the dyestuffs of Formula 1 in anauxiliary layer or, in particular, in a layer adjacent to thelight-sensitive layer.

The dyestuffs of Formulal are at the same time very fast to difiusion,easily soluble in water, insensitive to calcium ions and capable ofbeing bleached completely to white.

The dyestuffs in accordance with the invention also offer manypossibilities of variation of spectral properties and are characterizedby very pure and brilliant shades as well as by a surprisingly highstrength of colour.

The extremely favourable course of the spectral absorption curve allowsthese purple dyestuffs to be combined in various ways with in each casea suitable yellow and blue-green dyestuff. As a result, grey shadeswhich appear neutral are obtained throughout the whole density range forthe eye.

The dyestuffs of Formula 1 are characterized in particular by a highdegree of light fastness, strength of colour, resistance to diffusionand water solubility, as well as by a coourimetrically favorable form ofthe absorption spectrum in visible light.

EXAMPLE OF MANUFACTURE (1.1) 11.5 g. 3-aminoacetanilide-4-sulphonic acidare diazotised in 100 ml. water and 10 ml. 35% hydrochloric acid in thenormal way at C. with 12.5 ml. 4 N.

sodium nitrite solution.

After destruction of the excess nitrite, the diazo solu tion is added at58 C. and a pH of 3.5 to a suspension of 19.0 g. of a compound ofFormula 19.14 in a solution of 10.0 g. crystallised sodium acetate in100 ml. water. After 3 hours the cooling bath is removed and the mixtureis stirred for 12 hours at room temperature.

Heating is carried out for minutes at 65 C. and the dyestutf of theFormula 101.1 which separates out as a dark brown powder is filtered offat '40" C. The yield is almost quantitative.

- 101.1 Hots -0H NH-COCH:

I l IIIH HOQS (1.2) 6.1 g. of the product of Formula101.1 are stirred ina mixture of 50 ml. water and 50 ml. 35% hydroohloric acid for 8 hoursat 60 C. Filtering is carried out, then washing successively with waterand isopropanol, 4.7 g. (83%) dyestuff of the Formula 101.2 beingobtained in the form of a red powder.

(101.2) HQSIS OH l wm N=N 1 NH HOKS Column 1 is the formula numberColumn 2 islthe absorption maximum in mm.

(a) measured in dimethylformamide/Water 1:1 (b) measured in gelatine.

The radicals R R R R and M are substituents in the formula TABLE1G0ntinued R12 R13 R14 R15 M7 121 so 2H H H H 516 526 122 H H 803E H 533550 -o 0- o o o 0 12s H H 80311 H 537 546 -0 c s 02- c o- 127 cm H 01 H-o 0- 522+5a5 52s+547 12s H F H H 536 544-1-561 -0 cc o- 129 0H, H 01 H525+536 54o+552 -0 c 8 l0 0- V 130 CH3 H Cl H 525+536 538+552 -o OO-C 0-131 OH; H 01 H 531 52s+547 -o o o o- 132 0H, H H 01 532 554 -0 cl c 0-13a 0H, H H 01 526 540 -o 0 S l0 0- 134 cm H H 01 521+534 532+546 135 CH; H H O] 524 530 136 H so H 01 H 532 544 -0 o- 0 o-Qc 0- 137 OH; H s03H H 526 536 13s 0H, H s 03H H 526 550 -o 0- -o O-OO o- 139 CH3 H s OHH 526 540+568 -o NHOOHN -c 0- 140 H H F H 557 562 141 H H Br 540 564TABLE 1-C0ntinued (1) R R 3 R 4 E N17 (3.) (b

142 CH H 01 H 522+5fi2 532+557 O C H -G O 143 CH H 01 H 523+544 534+56 OC N 144 CH3 H C] H 531 560 ---O C- C 0- 145 CH B 01 H O 0 524-1642530+548 146 CH; H 01 H 5234-544 528+545 0 (:1 N=N C O whose absorptionmaxima, measured in dimethylformamide/water (1:1) are 530 and 552 nm.and, measured in gelatine, S50 and 585 nm.

EXAMPLE 1 There are pipetted into a test-tube 3.3 m1. 6% gelatinesolution, 2.0 ml. 1% aqueous solution of the hardener of the formula N i\C% $0311 1.0 m1. 1% aqueous solution of the purple dyestutf of theFormula 101 and 3.3 ml. silver bromide emulsion which contains 35 g.silver per litre, and the volume is brought up to 10.0 ml. withdeionised water. The solution is mixed thoroughly and is kept for 5minutes on a waterbath at 40 C.

The pouringsolution at 40 C. is poured onto a 13 cm. x 18 cm. substratedglass plate. After solidifying at 10 C., the plate is dried in a dryingcupboard with circulating air at 32 C.

A strip cut to 3.5 cm. x 18 cm. is exposed under a step wedge through ablue filter Kodak 2b +49 for 3 seconds with 50 lux/cmfi.

Then the following process is carried out:

(1) Develop for 10 minutes in a bath which contains per litre 1 g.p-methylaminophenol sulphate, 20 g. anhydrous sodium sulphite, 4 g.hydroquinone, 10 g. anhydrous sodium carbonate and 2 g. potassiumbromide;

(2) Soak for 2 minutes;

(3) Stop fix for 6 minutes in a bath which contains per litre 200 g.crystallised sodium thiosulphate, 15 g. anhydrous sodium sulphite, 25 g.crystallised sodium acetate and 13 ml. glacial acetic acid;

(4) Soak for 8 minutes;

(5) Colour bleach for 20 minutes in a bath which contains per litre 27.5ml. 96% sulphuric acid, 10 g. potassium iodide and 15 ml. of a solutionof 0.3 g. 2,3-dimethyl-6-aminoquinoxaline in 50 ml. ethanol;

(6) Soak for 4 minutes;

(7) Bleach residual silver for 8 minutes in a bath which contains perlitre 50 g. potassium ferric cyanide, 15 g. potassium bromide, 10 g.disodium phosphate and 14 g. monosodium phosphate;

(8) Soak for 6 minutes;

(9) Fix for 6 minutes as indicated in (3);

(10) Soak for 10 minutes.

A brilliant, light-fast purple wedge is obtained which is completelybleached to white at the point of the originallyhighest silver density.

Similar results are obtained on using one of the other dyestulfs inTable 1.

21 EXAMPLE 2 The following layers are applied successively to a whiteopaque acetate film provided with an adhesive layer:

(1) Red-sensitive silver bromide emulsion in gelatine containing thegreenish blue dyestufi' of the formula O-co-m: on cm 6 N=NN=N no 40in meno. out

(2) Colourless gelatine layer without silver halide.

(3) Green-sensitive silver bromide emulsion in gelatine containing thepurple dyestuif of Formula 129.

(4) Blue-sensitive silver bromide emulsion gelatine containing theyellow dyestuif of the formula The gelatine layers can also containadditives such as wetting agents, hardeners and stabilisers for thesilver halide. For the rest, the method is such that the individuallayers contain per square metre of film 0.5 g. of the relevant dyestufiand the amount of silver bromide corresponding to 1 to 1.2 g. silver.

This film is exposed under a coloured slide with red, green and bluecopying light. Then the copy is developed according to the instructiongiven in Example 1.

A light-fast, document-fast, positive image is obtained.

Similar results are obtained if another dyestufi of Table 1 is used inplace of the dyestufi of Formula 129.

EXAMPLE 3 There are pipetted into a test tube 3.3 ml. 6% gelatinesolution, 2.0 ml. 1% aqueous solution of the hardener of Formula 201,3.3 ml. silver bromide emulsion, containing per litre 35 g. silver, and1.4 ml. deionised water.

Thorough mixing is carried out and the tube is kept in a waterbath at 40C. for 5 minutes.

The pouring solution at 40 C. is poured onto a 13 cm. x 18 cm.substrated glass plate. After solidifying at C., the plate is dried at32 C. with circulating air in a drying cupboard.

There is then poured onto the dried layer at 40 C. a mixture of 3.3 ml.6% gelatine solution, 2.0 ml. 1% aqueous solution of the hardener ofFormula 201, 0.5 ml. 1% aqueous solution of the purple dyestutf ofFormula 130 and 4.2 ml. deionised water.

The result is allowed to solidify and dry as indicated above.

A strip cut to 3.5 cm. x 18 cm. is exposed under a step wedge through ablue filter Kodak 2b +49 for 10 seconds with 50 lux./cm.

Then the procedure set out in Example 1 is carried out.

A brilliant, very light-fast purple wedge is obtained which iscompletely bleached to white at the position of the originally highestsilver density.

Similar results are obtained if there is used instead of the dyestuif ofFormula 130 another dyestufi in Table 1.

EXAMPLE 4 A sample strip made and exposed using the purple dyestuff ofFormula 131 in accordance with Example 1 is processed as follows:

1) Develop for 5 minutes in a bath containing per litre l g.p-methylaminophenolsulphate,, 20 g. anhydrous sodium sulphite, 4 g.hydroquinone, 10 g. anhydrous sodium carbonate, 2 g. potassium bromideand 3 g. sodium rhodanide;

(2) Soak for 2 minutes;

(3) Treat for 2 minutes in a reversing bath containing per litre 5 g.potassium bichromate and 5 ml. 96% sulphuric acid;

(4) Soak for 4 minutes;

(5) Treat for 5 minutes in a bath containing per litre 50 g. anhydroussodium sulphite;

(6) Soak for 3 minutes;

(7) Develop for 4 minutes in a bath containing per litre 2 g.1-phenyl-3-pyrazolidone, 50 g. anhydrous sodium sulphite, 10 g.hydroquinone, 50 g. anhydrous sodium carbonate, 2 g. sodiumhexametaphosphate and 20 ml. of a 1% aqueous solution oftert.-butylaminoborane;

(8) Soak for 2 minutes;

(9) Continue to treat as indicated in (5) to (10) in Example 1.

A brilliant, highly light-fast purple wedge running oppositely to theoriginal pattern is obtained.

Similar results are obtained using one of the remaining dyestuffs ofTable 1.

What is claimed is:

1. A photographic light sensitive silver halide material which containson a support at least one layer with a dyestuif of the formula in whichX and X represent a sulfonic acid group or a hydrogen atom, A and A eachrepresent a benzene radical which is free from further substituents orcarries as a further substituent a halogen atom, a lower alkyl group, alower alkoxy group or a sulfonic acid group, R and R each represent ahalogen atom, a lower alkyl group, a trifluoromethyl group, a loweralkoxy group, a phenoxy group, a lower alkyl carbonyl group, acarboxylic acid amide group, a lower alkylsulfonyl group, a sulfonicacid amide group, a carboxylic acid group or a sulfonic acid group, Rand R each represents a hydrogen atom, a halogen atom, a lower alkoxygroup or a sulfonic acid group, and M represents a -CO group, aterephthaloyl group, an isophthaloyl group, abenzophenone-4,4'dicarbonyl group, a diphenylsulfone-4,4-dicarbonylgroup, a diphenylurea-4,4'-dicarbonyl group, an azo benzene-3,3-dicarbonyl group, a thiophene-2,5-dicarbonyl group, a pyridine-2,6- or3,5-dicarbonyl group, the azo groups present in the molecule beingarranged in the form of a straight chain.

2. A photographic material according to claim 1, that contains adyestutf of the formula 03 NHMPHN H0 Q :53 03B 110; HQ 3 Ba Ba in whichR represents a hydrogen atom, a halogen atom, a methyl group, a methoxygroup, a sulfonic acid group, R represents a sulfonic acid group, an HCOC- group or a halogen atom, at most one of R and R standing for asulfonic acid group.

23 3. A photographic material according to claim 1, that contains adyestufi of the formula H 0115 5 OH E E on n NE-Mg-HN ridi g N=N OaH H01EN B1 B4 3: 3a

in which R represents a halogen atom with an atomic number less than 53,a trifluoromethyl group, an H COC group, an H CO S group, a sulfonicacid group or a methoxy group, R represents a hydrogen atom, a halogenatom with an atomic number less than 53 or a methyl group.

4. A photographic material according to claim 1, that contains adyestutf of the formula H013 EOiE OB NHJfu-HN no as? QM E E0: OIB

on nn-m-mz no N=N Qatar NE H015 om an a mca in which M represents aterephthaloyl radical, an isophthaloyl radical, a pyridine-2,6- or-3,5-dicarbonyl radical or a thiophene-2,5-dicarbony1 radical.

6. A photographic material according to claim 1, that contains adyestufi of the formula caois Q bin; no. our an Hue-E in which Mrepresents a terephthaloyl radical, an isophthaloyl radical, apyridine-2,6- or -3,5-dicarbonyl radical or a thiophene-2,5-dicarbonylradical.

7. A photographic material according to claim 1, that contains adyestuflf of the formula non a sour on nrz-oe-O-co-Na no N- G N=N H04501E l N in which R represents one of the radicals of the formulae andOCCH3 I Br 8. A photographic material according to claim 1, thatcontains a dyestufif of the formula in which M represents a pyridineradical arranged symmetrically in relation to the bonds to the CO-groups and R represents one of the radicals of the formulae and FReferences Cited UNITED STATES PATENTS 7/1969 Anderau 9699 4/ 1972Piller 9699 J. TRAVIS BROWN, Primary Examiner US. Cl. X.R.

